Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/12—Esters of monohydric alcohols or phenols
  • C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/62—Monocarboxylic acids having ten or more carbon atoms; Derivatives thereof
  • C08F220/68—Esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/12—Polymerisation in non-solvents
  • C08F2/16—Aqueous medium
  • C08F2/22—Emulsion polymerisation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/04—Acids; Metal salts or ammonium salts thereof
  • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Definitions

• the present invention relates to emulsion polymers and to aqueous dispersions which comprise these emulsion polymers.
• the present invention further relates to processes for preparing these dispersions and emulsion polymers.
• Coating materials more particularly paints and varnishes, have for a long time been prepared synthetically.
• Many of these coating materials are based on what are called alkyd resins, which are prepared using polybasic acids, alcohols and fatty acids and/or fatty acid derivatives.
• alkyd resins are prepared using polybasic acids, alcohols and fatty acids and/or fatty acid derivatives.
• One particular group of these alkyd resins form crosslinked films on exposure to oxygen, the crosslinking taking place by oxidation with involvement of unsaturated groups.
• Many of these alkyd resins comprise organic solvents or dispersion media to allow the resins to be applied in a thin film to coating elements. The use of these solvents ought, however, to be abandoned on grounds of environmental protection and of occupational safety.
• Corresponding resins have therefore been developed based on aqueous dispersions, but their stability on storage is limited. Furthermore, the water absorption of many alkyd resins is too high, or their solvent resistance or their hardness is too low.
• compositions which comprise an alkyd resin which is modified with (meth)acrylate polymers and which is subsequently used in an emulsion polymerization.
• the compositions described are prepared over a number of steps, with the consequence that the resins described are very costly and inconvenient to prepare.
• a coating composition based on solution polymers based on vinyl monomers, for example, is described in DE-A-101 06 561. That composition, however, includes a high fraction of organic solvents.
• aqueous dispersions based on (meth)acrylate polymers.
• the publication DE-A-41 05 134 describes aqueous dispersions which can be used as binders in coating materials. The preparation of those binders, however, takes place over several stages, in which first a solution polymer is produced which, following neutralization, is used in an emulsion polymerization.
• DE-A-25 13 516 describes aqueous dispersions comprising polymers based on (meth)acrylates, where some of the (meth)acrylates contain unsaturated alcohol residues.
• a particular disadvantage of the dispersions described is their costly and inconvenient preparation, the polymers being obtained on the basis of (meth)acrylates by solution polymerization. In that case these polymers have a high fraction of acid groups, in the range from 5% to 20% by weight, based on the solution polymer.
• the publication DE-A-26 38 544 describes oxidatively drying aqueous dispersions which comprise emulsion polymers based on (meth)acrylates, with some of the (meth)acrylates used having unsaturated alcohol residues.
• chain transfer agents have been used to prepare the emulsion polymers, and so the solubility of the emulsion polymer is high.
• aqueous dispersions comprising oxidatively drying polymers are set out in F.-B. Chen, G. Bufkin, “Crosslinkable Emulsion Polymers by Autooxidation II”, Journal of Applied Polymer Science, Vol. 30, 4551-4570 (1985).
• the polymers contain 2% to 8% by weight of units derived from (meth)acrylates having unsaturated, long-chain alcohol residues. These polymers, however, do not contain any units obtained by polymerization of monomers containing acid groups. For many applications the shelf life of these dispersions and also the hardness of the coatings are inadequate.
• the document WO 2006/013061 describes dispersions which comprise particles based on (meth)acrylates.
• the monomer mixtures used to prepare the particles comprise (meth)acrylates which have been modified by unsaturated fatty acids. In the examples, however, no monomers which comprise acid groups are polymerized. Furthermore, the fraction of (meth)acrylates modified with unsaturated fatty acids is very high. Disadvantages of the dispersions described in WO 2006/013061 are more particularly their complex preparation and the high fraction of residual monomers. A minimum fraction of soluble emulsion polymer is not described in this publication.
• the prior art has also disclosed dispersions which, as well as polymers based on (meth)acrylates, can also comprise alkyd resins.
• the document WO 98/22545 describes polymers with units derived from (meth)acrylates having unsaturated alcohol residues. These polymers can be used together with alkyd resins.
• solvents are used in order to prepare coating materials from the polymers described.
• Aqueous dispersions are not described in WO 98/22545. Accordingly, these compositions are hampered by the disadvantages described above.
• JP 59011376 describes emulsion polymers based on (meth)acrylates.
• the dispersions for a solids content of approximately 40%, have a dynamic viscosity of at least 200 mPas.
• This publication does not specify a particle size. Owing to the high viscosity of the dispersion, however, it can be assumed that the emulsion polymers have a particle size below 40 nm.
• a disadvantage of the dispersions described in this publication is their short shelf life.
• the dispersions and emulsion polymers ought to have a very low residual monomer content.
• the intention was that the hardness of the coatings obtainable from coating materials with the emulsion polymers can be varied over a wide range. More particularly the intention was that particularly hard, scratch-resistant coatings can be obtained.
• a further object can be seen in the provision of emulsion polymers which can be used to obtain coating materials without volatile organic solvents.
• the coatings obtainable from the aqueous dispersions ought to have a high weathering stability, more particularly a high UV stability.
• the films obtainable from the aqueous dispersions ought after a short time to feature a low tack.
• the present invention accordingly provides an emulsion polymer comprising at least one (meth)acrylate segment which comprises
• the dispersions and emulsion polymers of the invention have a very low residual monomer content.
• the hardness of the coatings obtainable from dispersions of the invention with the emulsion polymers can be varied over a wide range. In one preferred modification, in accordance with the invention, it is possible more particularly to obtain particularly hard, scratch-resistant coatings.
• the coatings obtainable from the dispersions and emulsion polymers of the invention exhibit a surprisingly high solvent resistance, which is manifested more particularly in tests with methyl isobutyl ketone (MIBK) or ethanol.
• MIBK methyl isobutyl ketone
• the coatings obtained exhibit an outstanding classification in the context more particularly of experiments in accordance with the DIN 68861-1 furniture test. In this case the coatings can be cleaned even with non-polar solvents, more particularly with wash benzine, without the coating being irreversibly damaged as a result.
• Coating materials obtainable using the emulsion polymers of the invention generally require no volatile organic solvents. Furthermore, the dispersions of the invention exhibit a high level of storage stability, a long shelf life and very good storage properties. More particularly there is virtually no aggregate formed.
• the coatings obtainable from the aqueous dispersions exhibit a high level of weathering stability, more particularly a high UV stability.
• the films obtainable from the aqueous dispersions, furthermore, after a short time feature a low tack.
• the coating materials of the invention exhibit high wet-film stability and also an increased open time.
• the coatings obtainable from the dispersions of the invention exhibit, on numerous substrates, particularly high strength of adhesion, abrasion resistance and durability.
• Preferred coatings, and substrates coated with the coatings of the invention may be exposed, in particular, to high mechanical loads without the coating cracking.
• the dispersions and emulsion polymers of the invention can be prepared inexpensively on a large scale.
• the dispersions and emulsion polymers of the invention are eco-friendly and can be prepared and processed safely and without great cost and complexity.
• the dispersions of the invention exhibit a very high shear stability.
• the emulsion polymers of the invention comprise at least one (meth)acrylate segment.
• emulsion polymer denotes herein a macromolecular compound which can be obtained by emulsion polymerization.
• segment denotes the fact that the emulsion polymer comprises at least one section with repeating (meth)acrylate units.
• the emulsion polymer may consist of one segment thus constructed, or may have further segments.
• the emulsion polymers can be obtained preferably by means of free-radical addition polymerization.
• the weight fraction of units is a product of the weight fractions of corresponding monomers that are used for the preparation of the polymers.
• the weight fraction of the (meth)acrylate segment based on the weight of the emulsion polymer, is preferably at least 10% by weight, more preferably at least 20% by weight.
• the emulsion polymer preferably comprises at least 40%, more preferably at least 60% and very preferably at least 90% by weight of (meth)acrylates.
• the (meth)acrylate segment comprises 1 to 30%, preferably 5% to 25% and more preferably 10% to 20% by weight of units derived from (meth)acrylates which in the alkyl radical have at least one double bond and 8 to 40 carbon atoms, based on the total weight of the (meth)acrylate segment.
• (meth)acrylates encompasses methacrylates and acrylates and also mixtures of both.
• (Meth)acrylates which in the alkyl radical have at least one double bond and 8 to 40 carbon atoms are esters of (meth)acrylic acid whose alcohol residue has at least one double bond and 8 to 40 carbon atoms.
• the alkyl radical or alcohol residue may contain preferably 10 to 30 and more preferably 12 to 20 carbon atoms, it being possible for this radical to include heteroatoms, more particularly oxygen, nitrogen or sulphur atoms.
• the alcohol residue may have one, two, three or more double bonds.
• the polymerization conditions under which the emulsion polymer is prepared are preferably selected such as to maximize the fraction of the double bonds of the alcohol residue that are retained during the polymerization. This may be done, for example, by sterically hindering the double bonds present in the alcohol residue.
• the iodine number of the (meth)acrylates for use for preparing the emulsion polymers and containing in the alkyl radical at least one double bond and 8 to 40 carbon atoms is preferably at least 40, more preferably at least 80 and very preferably at least 140 g iodine/100 g (meth)acrylate.
• R represents hydrogen or methyl and R 1 denotes a linear or branched radical having 8 to 40 carbon atoms that contains at least one double bond.
• (Meth)acrylates which in the alkyl radical have at least one double bond and 8 to 40 carbon atoms may be obtained, for example, by esterification of (meth)acrylic acid, reaction of (meth)acryloyl halides or transesterification of (meth)acrylates with alcohols which have at least one double bond and 8 to 40 carbon atoms. These reactions are set out in, for example, Ullmann's Encyclopaedia of Industrial Chemistry, 5th edition on CD-ROM, or F.-B. Chen, G. Bufkin, “Crosslinkable Emulsion Polymers by Autooxidation I”, Journal of Applied Polymer Science, Vol. 30, 4571-4582 (1985).
• the alcohols that are suitable for this purpose include, among others, octenol, nonenol, decenol, undecenol, dodecenol, tridecenol, tetradecenol, pentadecenol, hexadecenol, heptadecenol, octadecenol, nonadecenol, eicosenol, docosenol, octan-dien-ol, nonan-dien-ol, decan-dien-ol, undecan-dien-ol, dodecan-dien-ol, tridecan-dien-ol, tetradecan-dien-ol, pentadecan-dien-ol, hexadecan-dien-ol, heptadecan-dien-ol, octadecan-dien-ol, nonadecan-dien
• fatty alcohols are in some cases available commercially or can be obtained from fatty acids, that reaction being set out in, for example, F.-B. Chen, G. Bufkin, Journal of Applied Polymer Science, Vol. 30, 4571-4582 (1985).
• the preferred (meth)acrylates obtainable by this process include, more particularly, octadecan-dien-yl (meth)acrylate, octadecan-trien-yl (meth)acrylate, hexadecenyl (meth)acrylate, octadecenyl (meth)acrylate and hexadecan-dien-yl (meth)acrylate.
• (meth)acrylates which in the alkyl radical have at least one double bond and 8 to 40 carbon atoms can also be obtained by reacting unsaturated fatty acids with (meth)acrylates which have reactive groups in the alcohol residue.
• the reactive groups include, more particularly, hydroxyl groups and also epoxy groups.
• hydroxyalkyl (meth)acrylates such as 3-hydroxypropyl (meth)acrylate, 3,4-dihydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2,5-dimethyl-1,6-hexanediol (meth)acrylate, 1,10-decanediol (meth)acrylate; or (meth)acrylates containing epoxy groups, an example being glycidyl (meth)acrylate, as reactants for preparing the aforementioned (meth)acrylates.
• hydroxyalkyl (meth)acrylates such as 3-hydroxypropyl (meth)acrylate, 3,4-dihydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2,5-dimethyl-1,6-hexanediol (meth)acrylate, 1,10-decanedi
• Suitable fatty acids for reaction of the aforementioned (meth)acrylates are in many cases available commercially and are obtained from natural sources. They include, among others, undecylenic acid, palmitoleic acid, oleic acid, elaidinic acid, vaccenic acid, eicosenoic acid, cetoleic acid, erucic acid, nervonic acid, linoleic acid, linolenic acid, arachidonic acid, timnodonic acid, clupanodonic acid and/or cervonic acid.
• the preferred (meth)acrylates which are obtainable by this process include, more particularly, (meth)acryloyloxy-2-hydroxypropyl-linoleic ester, (meth)acryloyloxy-2-hydroxypropyl-linolenic ester and (meth)acryloyloxy-2-hydroxypropyl-oleic ester.
• the (meth)acrylates with at least one double bond that are set out above may be used individually or as a mixture of two or more (meth)acrylates.
• (meth)acrylate segments which comprise a high fraction of units derived from (meth)acryloyloxy-2-hydroxypropyl-linoleic ester.
• (meth)acrylate segments which comprise at least 20%, preferably at least 40% and very preferably at least 50% by weight of units derived from (meth)acryloyloxy-2-hydroxypropyl-linoleic ester, based on the weight of the units derived from (meth)acrylates which in the alkyl radical have at least one double bond and 8 to 40 carbon atoms.
• the (meth)acrylate segment contains 45% to 80%, more preferably 55% to 70%, by weight of units derived from (meth)acryloyloxy-2-hydroxypropyl-linoleic ester, based on the weight of the units derived from (meth)acrylates which in the alkyl radical have at least one double bond and 8 to 40 carbon atoms.
• (meth)acrylate segments which comprise at least 5%, preferably at least 10% and more preferably at least 15% by weight of units derived from (meth)acryloyloxy-2-hydroxypropyl-oleic ester, based on the weight of the units derived from (meth)acrylates which in the alkyl radical have at least one double bond and 8 to 40 carbon atoms.
• the polymer contains 15% to 45%, more preferably 20% to 35%, by weight of units derived from (meth)acryloyloxy-2-hydroxypropyl-oleic ester, based on the weight of the units derived from (meth)acrylates which in the alkyl radical have at least one double bond and 8 to 40 carbon atoms.
• weight ratio of units derived from (meth)acryloyloxy-2-hydroxypropyl-linoleic ester to units derived from (meth)acryloyloxy-2-hydroxypropyl-oleic ester is greater than or equal to 1, this weight ratio being more preferably in the range from 8:1 to 1:1, with particular preference 5:1 to 3:2.
• the (meth)acrylate segment of the emulsion polymers of the invention comprises 0.1% to 10%, preferably 0.5% to 8% and more preferably 1% to 5% by weight of units derived from monomers containing acid groups, based on the total weight of the (meth)acrylate segment.
• Monomers containing acid groups are compounds which can be copolymerized preferably free-radically with the (meth)acrylates set out above. They include, for example, monomers having a sulphonic acid group, such as vinylsulphonic acid, for example; monomers having a phosphonic acid group, such as vinylphosphonic acid, for example; and unsaturated carboxylic acids, such as methacrylic acid, acrylic acid, fumaric acid and maleic acid, for example. Methacrylic acid and acrylic acid are particularly preferred.
• the monomers containing acid groups can be used individually or as a mixture of two, three or more monomers containing acid groups.
• the (meth)acrylate segment of the emulsion polymers of the invention further comprises 50% to 98.9%, preferably 60% to 95% and more preferably 70 to 90% by weight of units derived from (meth)acrylates having 1 to 6 carbon atoms in the alkyl radical, based on the total weight of the (meth)acrylate segment.
• R represents hydrogen or methyl and R 2 denotes a linear or branched radical having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms.
• (meth)acrylates deriving from saturated alcohols such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate and pentyl (meth)acrylate, hexyl (meth)acrylate;
• mixtures comprising methacrylates and acrylates are particularly preferred.
• mixtures of methyl methacrylate and acrylates having 2 to 6 carbons such as ethyl acrylate, butyl acrylate and hexyl acrylate.
• the (meth)acrylate segment of the emulsion polymers of the invention may have units derived from comonomers. These comonomers differ from the units of the emulsion polymer that have been set out above, but can be copolymerized with the monomers set out above.
• (meth)acrylates having at least 7 carbon atoms in the alkyl radical and deriving from saturated alcohols such as, for example, 2-ethylhexyl (meth)acrylate, heptyl (meth)acrylate, 2-tert-butylheptyl (meth)acrylate, octyl (meth)acrylate, 3-isopropylheptyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, 5-methylundecyl (meth)acrylate, dodecyl (meth)acrylate, 2-methyldodecyl (meth)acrylate, tridecyl (meth)acrylate, 5-methyltridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate,
• the fraction of units derived from comonomers can be varied in accordance with the intended use and profile of properties of the polymer. In general this fraction can be situated in the range from 0% to 45%, preferably 2% to 30% and more preferably 3% to 10%, by weight, based on the total weight of the (meth)acrylate segment.
• the weathering resistance of the coatings may be improved more particularly by reducing the fraction of styrene monomers in the coating material or in the emulsion polymer, and so particularly UV-resistant coatings may be obtained by means of a styrene-free coating material.
• the emulsion polymer with at least one (meth)acrylate segment contains preferably not more than 30%, more preferably not more than 15%, by weight of units derived from styrene, substituted styrenes having an alkyl substituent in the side chain, substituted styrenes having an alkyl substituent in the ring and/or halogenated styrenes, based on the total weight of the (meth)acrylate segment.
• Particularly scratch-resistant and solvent-resistant coatings can be obtained more particularly by the emulsion polymer with at least one (meth)acrylate segment comprising not more than 10% by weight of units derived from (meth)acrylates which are obtainable by reacting saturated fatty acids with at least one (meth)acrylate which has reactive groups in the alcohol residue, based on the total weight of the (meth)acrylate segment.
• emulsion polymers which comprise preferably 0.05% to 5%, more preferably 0.1 to 3%, by weight of units derived from (meth)acrylates which are obtainable by reacting saturated fatty acids with at least one (meth)acrylate which has reactive groups in the alcohol residue, based on the total weight of the (meth)acrylate segment.
• emulsion polymers which comprise preferably 0.05% to 5%, more preferably 0.1 to 3%, by weight of units derived from (meth)acrylates which are obtainable by reacting saturated fatty acids with at least one (meth)acrylate which has reactive groups in the alcohol residue, based on the total weight of the (meth)acrylate segment.
• Saturated fatty acids which can be reacted with a (meth)acrylate comprising at least one reactive group in the alcohol residue, preferably glycidyl (meth)acrylate may comprise preferably 10 to 26, more preferably 12 to 22, carbon atoms.
• the saturated fatty acids having 10 to 26 carbon atoms include more particularly caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, arachidic acid, behenic acid, lignoceric acid, cerotinic acid, palmitoleic acid and stearic acid.
• the emulsion polymer can have a fraction of 2% to 60%, more preferably 10% to 50% and very preferably 20% to 40%, by weight, based on the weight of the emulsion polymer, which is soluble in tetrahydrofuran (THF) at 20° C.
• THF tetrahydrofuran
• a sample of the polymer with at least one (meth)acrylate segment that has been dried in the absence of oxygen is stored in 200 times the amount of solvent, based on the weight of the sample, at 20° C. for 4 h.
• the sample for example, can be dried under nitrogen or under reduced pressure.
• the solution is separated, by filtration for example, from the insoluble fraction.
• the weight of the residue is determined.
• a 0.5 g sample of an emulsion polymer dried under reduced pressure can be stored in 150 ml of THF for 4 hours.
• an emulsion polymer may exhibit swelling of at least 1000%, more preferably at least 1400% and very preferably at least 1600% in tetrahydrofuran (THF) at 20° C.
• the upper limit on the swelling is not critical per se, the swelling preferably being not more than 5000%, more preferably not more than 3000% and very preferably not more than 2500%.
• THF tetrahydrofuran
• a sample of the emulsion polymer that has been dried in the absence of oxygen is stored in 200 times the amount of THF at 20° C. for 4 hours. As a result the sample swells. The swollen sample is separated from the supernatant solvent. Subsequently the solvent is removed from the sample.
• a major fraction of the solvent can be evaporated at room temperature (20° C.). Solvent residues can be removed in a drying oven (140° C.), generally over the course of 1 hour. From the weight of the solvent absorbed by the sample and the weight of the dry sample the swelling is obtained. Furthermore, the difference in the weight of the sample prior to the swelling experiment and the weight of the dried sample after the swelling experiment produces the soluble fraction of the emulsion polymer.
• the particle radius of the emulsion polymer is at least 50 nm.
• the radius of the particles is situated preferably in the range from 60 nm to 500 nm, more preferably 70 to 150 nm and very preferably 75 to 100 nm.
• the radius of the particles can be determined by means of PCS (Photon Correlation Spectroscopy), the data given relating to the d50 value (50% of the particles are smaller, 50% are larger). This can be done using, for example, a Beckman Coulter N5 Submicron Particle Size Analyzer.
• the glass transition temperature of the (meth)acrylate segment is situated preferably in the range from ⁇ 30° C. to 70° C., more preferably in the range from ⁇ 20 to 40° C. and very preferably in the range from 0 to 25° C.
• the glass transition temperature may be influenced via the nature and the fraction of the monomers used to prepare the (meth)acrylate segment.
• the glass transition temperature, Tg, of the polymer may be determined in a known way by means of Differential Scanning Calorimetry (DSC).
• DSC Differential Scanning Calorimetry
• the glass transition temperature Tg may also be calculated approximately in advance by means of the Fox equation. According to Fox T. G., Bull. Am. Physics Soc. 1, 3, page 123 (1956) it is the case that
• Tg x 1 Tg 1 + x 2 Tg 2 + ... + x n Tg n
• x n represents the mass fraction (% by weight/100) of the monomer n
• Tg n identifies the glass transition temperature, in kelvins, of the homopolymer of the monomer n. Further useful information can be found by the skilled person in the Polymer Handbook, 2nd Edition, J. Wiley & Sons, New York (1975), which gives Tg values for the most common homopolymers.
• the architecture of the emulsion polymer/(meth)acrylate segment is not critical.
• the emulsion polymers/(meth)acrylate segments may accordingly comprise random copolymers, gradient copolymers, block copolymers and/or graft copolymers.
• Block copolymers and gradient copolymers can be obtained, for example, by discontinuously altering the monomer composition during chain propagation.
• the emulsion polymer comprises a random copolymer in which the monomer composition over the polymerization is substantially constant. Since, however, the monomers may have different copolymerization parameters, the precise composition may fluctuate over the polymer chain of the emulsion polymer/(meth)acrylate segment.
• the emulsion polymer may constitute a homogeneous polymer which, for example, in an aqueous dispersion forms particles having a consistent composition.
• the emulsion polymer may be composed of one or more (meth)acrylate segments which comprise 1% to 30% by weight of units derived from (meth)acrylates which in the alkyl radical have at least one double bond and 8 to 40 carbon atoms, 0.1% to 10% by weight of units derived from monomers containing acid groups, and 50% to 98.9% by weight of units derived from (meth)acrylates having 1 to 6 carbon atoms in the alkyl radical, based on the weight of the (meth)acrylate segment.
• the emulsion polymer may constitute a core-shell polymer, which may have one, two, three or more shells.
• the (meth)acrylate segment preferably forms the outermost shell of the core-shell polymer.
• the shell may be connected to the core or to the inner shells, by covalent bonds.
• the shell may also be polymerized onto the core or onto an inner shell.
• the (meth)acrylate segments may in many cases be separated and isolated from the core by means of suitable solvents.
• the weight ratio of (meth)acrylate segment to core may be situated preferably in the range from 2:1 to 1:6, more preferably 1:1 to 1:3.
• the core may be formed preferably of polymers comprising 50% to 100%, preferably 60% to 90%, by weight of units derived from (meth)acrylates. Preference here is given to esters of (meth)acrylic acid whose alcohol residue comprises preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms and very preferably 1 to 10 carbon atoms.
• (meth)acrylates deriving from saturated alcohols, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate and hexyl (meth)acrylate.
• saturated alcohols such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate and hexyl (meth)acrylate.
• the core can be prepared using a mixture which comprises methacrylates and acrylates.
• methacrylates and acrylates can be prepared using a mixture which comprises methacrylates and acrylates.
• mixtures of methyl methacrylate and acrylates having 2 to 6 carbons such as ethyl acrylate, butyl acrylate and hexyl acrylate.
• the polymers of the core may comprise the comonomers set out above.
• the core may be crosslinked. This crosslinking may be achieved through the use of monomers having two, three or more free-radically polymerizable double bonds.
• the shell of an emulsion polymer of the present invention that comprises the (meth)acrylate segment may comprise preferably 15% to 28% by weight of units derived from (meth)acrylates which in the alkyl radical have at least one double bond and 8 to 40 carbon atoms.
• the core may preferably have a glass transition temperature in the range from ⁇ 30 to 200° C., more preferably in the range from ⁇ 20 to 150° C.
• the shell which is formed preferably by the (meth)acrylate segment of the emulsion polymer of the invention, may preferably have a glass transition temperature in the range from ⁇ 30° C. to 70° C., more preferably in the range from ⁇ 20 to 40° C. and very preferably in the range from 0 to 25° C.
• the glass transition temperature of the core may be greater than the glass transition temperature of the shell.
• Judiciously the glass transition temperature of the core may be at least 10° C., preferably at least 20° C., above the glass transition temperature of the shell.
• the iodine number of the emulsion polymer of the invention is preferably in the range from 1 to 150 g iodine per 100 g emulsion polymer, more preferably in the range from 2 to 100 g iodine per 100 g emulsion polymer and very preferably 5 to 40 g iodine per 100 g emulsion polymer, measured in accordance with DIN 53241-1.
• the iodine number may be measured more particularly on the basis of a dispersion of the invention.
• the emulsion polymer may have an acid number in the range from 0.1 to 40 mg KOH/g, preferably 1 to 20 mg KOH/g and very preferably in the range from 2 to 10 mg KOH/g.
• the acid number may be determined in accordance with DIN EN ISO 2114 from a dispersion.
• the hydroxyl number of the emulsion polymer is situated preferably in the la range from 0 to 200 mg KOH/g, more preferably 1 to 100 mg KOH/g and very preferably in the range from 3 to 50 mg KOH/g.
• the hydroxyl number may be determined in accordance with ASTM E222 from a dispersion.
• the emulsion polymers of the invention can be obtained by known methods of emulsion polymerization, which are set out in sources including Ullmann's Encyclopaedia of Industrial Chemistry, Fifth Edition. To do this the general approach is to prepare an aqueous phase which as well as water may include typical additives, more particularly emulsifiers and protective colloids for stabilizing the emulsion.
• This aqueous phase is then admixed with monomers, and polymerization is carried out in the aqueous phase.
• the dispersing of the monomer phase in the aqueous phase can take place using known agents. These include, more particularly, mechanical methods and also the application of ultrasound.
• the monomer mixture for preparing the emulsion polymers of the invention comprises preferably
• the monomer mixture more preferably contains 1% to 5% by weight of monomers containing acid groups.
• Core-shell polymer here stands for a polymer prepared by a two-stage or multistage emulsion polymerization, without the core-shell structure having been shown by means, for example, of electron microscopy. Monitoring of the progress of the polymerization reaction in each step can be effected in a known way, such as by gravimetry or gas chromatography, for example.
• the monomer mixture for preparing the core comprises preferably 50% to 100% by weight of (meth)acrylates, particular preference being given to the use of a mixture of acrylates and methacrylates.
• the core After the core has been prepared, it is possible to graft or to polymerize onto the core, preferably, a monomer mixture which comprises 15% to 28% by weight of (meth)acrylates which in the alkyl radical have at least one double bond and 8 to 40 carbon atoms.
• the emulsion polymerization is conducted preferably at a temperature in the range from 0 to 120° C., more preferably in the range from 30 to 100° C.
• Polymerization temperatures which have proved to be especially favourable in this context are temperatures in the range from greater than 60 to less than 90° C., judiciously in the range from greater than 70 to less than 85° C., preferably in the range from greater than 75 to less than 85° C.
• the polymerization is initiated with the initiators that are customary for emulsion polymerization.
• Suitable organic initiators are, for example, hydroperoxides such as tert-butyl hydroperoxide or cumene hydroperoxide.
• Suitable inorganic initiators are hydrogen peroxide and also the alkali metal salts and the ammonium salts of peroxodisulphuric acid, more particularly ammonium, sodium and potassium peroxodisulphate.
• Suitable redox initiator systems are, for example, combinations of tertiary amines with peroxides or sodium disulphite and alkali metal salts and the ammonium salts of peroxodisulphuric acid, more particularly sodium and potassium peroxodisulphate.
• the stated initiators may be used both individually and in a mixture. They are preferably used in an amount of 0.05% to 3.0% by weight, based on the total weight of the monomers of the respective stage. It is also possible with preference to carry out the polymerization with a mixture of different polymerization initiators having different half-lives, in order to keep the flow of free radicals constant over the course of the polymerization and also at different polymerization temperatures.
• Stabilization of the batch is accomplished preferably by means of emulsifiers and/or protective colloids.
• the emulsion is preferably stabilized by emulsifiers, in order to obtain a low dispersion viscosity.
• the total amount of emulsifier is preferably 0.1% to 15% by weight, more particularly 1% to 10% by weight and more preferably 2% to 5% by weight, based on the total weight of the monomers used. In accordance with one particular aspect of the present invention it is possible to add a portion of the emulsifiers during the polymerization.
• Particularly suitable emulsifiers are anionic or nonionic emulsifiers or mixtures thereof, more particularly
• the particularly preferred anionic emulsifiers include, more particularly, fatty alcohol ether sulphates, diisooctyl sulphosuccinate, lauryl sulphate, C15-paraffinsulphonate, it being possible to use these compounds generally in the form of the alkali metal salt, more particularly the sodium salt.
• These compounds may be obtained commercially, more particularly, under the commercial designations Disponil® FES 32, Aerosol® OT 75, Texapon® K1296 and Statexan® K1 from the companies Cognis GmbH, Cytec Industries, Inc. and Bayer AG.
• Judicious nonionic emulsifiers include tert-octylphenol ethoxylate with 30 ethylene oxide units and fatty alcohol polyethylene glycol ethers which have preferably 8 to 20 carbon atoms in the alkyl radical and 8 to 40 ethylene oxide units. These emulsifiers are available commercial under the commercial designations Triton® X 305 (Fluka), Tergitol® 15-S-7 (Sigma-Aldrich Co.), Marlipal® 1618/25 (Sasol Germany) and Marlipal® O 13/400 (Sasol Germany).
• the weight ratio of anionic emulsifier to nonionic emulsifier can judiciously be in the range from 20:1 to 1:20, preferably 2:1 to 1:10 and more preferably 1:1 to 1:5.
• Mixtures which have proven to be especially appropriate are those comprising a sulphate, more particularly a fatty alcohol ether sulphate, a lauryl sulphate, or a sulphonate, more particularly a diisooctyl sulphosuccinate or a paraffin sulphonate, as anionic emulsifier, and an alkylphenol ethoxylate or a fatty alcohol polyethylene glycol ether having in each case preferably 8 to 20 carbon atoms in the alkyl radical and 8 to 40 ethylene oxide units, as nonionic emulsifier.
• a sulphate more particularly a fatty alcohol ether sulphate, a lauryl sulphate, or a sulphonate, more particularly a diisooctyl sulphosuccinate or a paraffin sulphonate, as anionic emulsifier
• emulsifiers can also be used in a mixture of protective colloids.
• Suitable protective colloids include partially hydrolysed polyvinyl acetates, polyvinylpyrrolidones, carboxymethyl-, Methyl-, hydroxyethyl and hydroxypropyl-cellulose, starches, proteins, poly(meth)acrylic acid, poly(meth)acrylamide, polyvinylsulphonic acids, melamine-formaldehyde sulphonates, naphthalene-formaldehyde sulphonates, styrene-maleic acid and vinyl ether-maleic acid copolymers.
• protective colloids are used they are used preferably in an amount of 0.01 to 1.0% by weight, based on the total amount of the monomers.
• the protective colloids may be included in the initial charge before the start of the polymerization, or metered in.
• the initiator may be included in the initial charge or metered in. It is also possible, furthermore, to include a portion of the initiator in the initial charge and to meter in the remainder.
• the polymerization is preferably started by heating the batch to the polymerization temperature and metering in the initiator, preferably in aqueous solution.
• the metered feeds of emulsifier and monomers may be carried out separately or as a mixture.
• the approach taken is to premix emulsifier and monomer in a mixer upstream of the polymerization reactor.
• the remainders of emulsifier and of monomer which have not been included in the initial charge are metered in separately from one another after the start of the polymerization. With preference it is possible to commence the metered feed 15 to 35 minutes after the start of the polymerization.
• Emulsion polymers having a high fraction of insoluble polymers can be obtained in the manner set out above, the reaction parameters for obtaining a high molecular weight being known. Thus it is possible more particularly in this context to omit the use of molecular weight regulators.
• One of the ways in which the adjustment of the particle radii can be influenced is via the fraction of emulsifiers. The higher this fraction, more particularly at the beginning of the polymerization, the smaller the particles obtained.
• aqueous dispersions obtained by the process of the invention can be used as coating materials. Accordingly, aqueous dispersions are a further subject of the present invention.
• the aqueous dispersions preferably have a solids content in the range from 10% to 70% by weight, more preferably 20% to 60% by weight.
• the dispersion may judiciously have a dynamic viscosity within the range from 0.1 to 180 mPas, preferably 1 to 80 mPas, and very preferably 5 to 20 mPas, measured in accordance with DIN EN ISO 2555 at 25° C. (Brookfield).
• aqueous dispersions of the invention may be provided in a known manner with additives or further components for adapting the properties of the coating material to specific requirements.
• additional substances include, more particularly, drying assistants, known as siccatives, and flow improvers, pigments and dyes.
• the coating materials of the invention preferably have a minimum film formation temperature of not more than 50° C., with particular preference not more than 35° C. and very particular preference not more than 25° C., a temperature which can be measured in accordance with DIN ISO 2115.
• siccatives include, more particularly, organometallic compounds, examples being metal soaps of transition metals, such as cobalt, manganese, lead and zirconium, for example; alkali metals or alkaline earth metals, such as lithium, potassium and calcium, for example. Examples that may be mentioned include cobalt naphthalate and cobalt acetate.
• the siccatives can be used individually or as a mixture, in which case particular preference is given more particularly to mixtures which comprise cobalt salts, zirconium salts and lithium salts.
• the aqueous dispersions of the present invention can be used more particularly as coating materials or as additives for them.
• Such materials include, more particularly, paints and varnishes, impregnating compositions, adhesives and/or primer systems.
• the aqueous dispersions can be employed for producing paints, varnishes or impregnating compositions for applications on wood and/or metal.
• the coatings obtainable from the coating materials of the invention exhibit high solvent resistance: more particularly, only small fractions are dissolved from the coating by solvents.
• Preferred coatings exhibit a high resistance, more particularly, to methyl isobutyl ketone (MIBK).
• MIBK methyl isobutyl ketone
• the weight loss after treatment with MIBK amounts preferably to not more than 50% by weight, more preferably not more than 35% by weight.
• the absorption of MIBK amounts preferably to not more than 300% by weight, with particular preference not more than 250% by weight, based on the weight of the coating employed. These values are measured at a temperature of approximately 25° C. and over an exposure time of at least 4 hours, the coating subjected to measurement being a fully dried coating. This drying takes place in the presence of oxygen, air for example, in order to allow crosslinking.
• the coatings obtained from the coating materials of the invention display a high mechanical stability.
• the pendulum hardness is preferably at least 20 s, more preferably at least 25 s, measured in accordance with DIN ISO 1522.
• a 2 l glass reactor which had a water bath heating facility and was equipped with a blade stirrer was charged with 230 g of water and 0.3 g of Disponil FES 32 (30% form) and this initial charge was heated to 80° C. and admixed with 0.3 g of ammonium peroxodisulphate (APS) in solution in 10 g of water. 5 minutes after the addition of the APS, the emulsion prepared beforehand was metered in over the course of 240 minutes (interval: 3 minutes' feed, 4 minutes' pause, 237 minutes' feed of remainder).
• APS ammonium peroxodisulphate
• the batch was stirred at 80° C. for 1 hour. Thereafter it was cooled to room temperature and the dispersion was filtered through VA screen fabric of 0.09 mm mesh size.
• the emulsion prepared had a solids content of 40 ⁇ 1%, a pH of 2.6, a viscosity of 15 mPas and an r N5 value of 83 nm.
• the properties of the resulting coating material were investigated by a variety of methods. On dried films, experiments relating to the solvent resistance, water absorption and hardness were carried out for this purpose.
• the solvent resistance was determined using methyl isobutyl ketone (MIBK), with a sample being swollen with MIBK at room temperature for 4 hours. Thereafter the sample was taken from the solvent and excess solvent was removed. Subsequently the solvent was dried at about 140° C. for 1 hour. The fraction of the sample that is removed by the solvent is calculated from the weight loss.
• MIBK methyl isobutyl ketone
• the water absorption can be determined using a specimen of untreated solid pine (dimensions: 45-50 mm ⁇ 45-50 mm ⁇ 17 mm). The specimen was provided with a layer of varnish and placed in water at room temperature, with only the coated surface in contact with the water. The water absorption is calculated from the increase in weight of the specimen.
• the hardness of the coating which typically constitutes a measure of the scratch resistance, was investigated with the pencil hardness test and with the pendulum test.
• the tensile strength of the films which typically represents a measure of the mechanical strength of the coating, was determined in accordance with DIN EN ISO 527, part 3.
• Example 1 was essentially repeated, but using 80 g of methacryloyloxy-2-hydroxypropyl-oleic ester.
• the methacryloyloxy-2-hydroxypropyloleic ester was obtained by reaction of oleic acid with glycidyl methacrylate.
• the emulsion prepared had a solids content of 40 ⁇ 1%, a pH of 2.5, a viscosity of 16 mPas and an r N5 value of 71 nm.
• a 2 l glass reactor which had a water bath heating facility and was equipped with a blade stirrer was charged with 230 g of water and 0.3 g of Disponil FES 32 (30% form) and this initial charge was heated to 80° C. and admixed with 0.3 g of ammonium peroxodisulphate (APS) in solution in 10 g of water. 5 minutes after the addition of the APS, the emulsion prepared beforehand was metered in over the course of 240 minutes (interval: 3 minutes' feed, 4 minutes' pause, 237 minutes' feed of remainder).
• APS ammonium peroxodisulphate
• the batch was stirred at 80° C. for 1 hour. Thereafter it was cooled to room temperature and the dispersion was filtered through VA screen fabric of 0.09 mm mesh size.
• Inventive Example 1 was essentially repeated, the dispersion being prepared via a miniemulsion process.
• 400 g of butyl acrylate, 390 g of methyl methacrylate, 200 g of methacryloyloxy-2-hydroxypropyl-linoleic ester and 10 g of methacrylic acid were emulsified with 20 g of sodium dodecyl sulphate.
• As a hydrophobic agent 4% of hexadecane were added additionally.
• the polymerization was initiated with 1% of AIBN at 75° C.
• the dispersion obtained had an r N5 value of 51 nm and a pH of 4.1.
• a coating formed from the dispersion showed a weight loss in MIBK of 11.7%, a water absorption after 24 h of 22.8% and a tensile strength of 5.1 MPa.
• Inventive Example 1 was essentially repeated, the dispersion being prepared via a miniemulsion process.
• 400 g of butyl acrylate, 390 g of methyl methacrylate, 200 g of methacryloyloxy-2-ethyl-linoleic ester and 10 g of methacrylic acid were emulsified with 20 g of sodium dodecyl sulphate.
• the methacryloyloxy-2-ethyl-linoleic ester was obtained by reaction of linoleic acid with hydroxyethyl methacrylate.
• As a hydrophobic agent 4% of hexadecane were added additionally.
• the polymerization was initiated with 1% of AIBN at 75° C.
• the dispersion obtained had an r N5 value of 65 nm and a pH of 3.9.
• a coating formed from the dispersion showed a weight loss in MIBK of 13.6%, a water absorption after 24 h of 9.2% and a tensile strength of 2.8 MPa.

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